TW495536B - Epoxy resin compositions - Google Patents

Abstract

The present invention provides a coating composition comprising one or more curable resins which contain, among the resins, free acrylic moieties and free or reacted epoxy moieties, and a ketone blocked polyamine type curing agent, the ingredients being chosen to provide in the coating after curing, more than 50% by weight of cured epoxy groups and less than 50% by weight of cured acrylic groups.

Description

495536 A7 __B7 8 \, V. Description of the invention (丨) 1 y [Explanation of the invention] The present invention relates to an epoxy resin composition, which is suitable for coatings and adhesives. Epoxy coating compositions usually contain a solid or semi-solid epoxy resin in an organic solvent. When the solvent has evaporated, the solid or near-solid residue forms a film, even before a significant reaction with the hardener occurs. There is an increasing need to reduce the amount of organic solvents used in this coating, resulting in a so-called low volatile organic content (V.O.C). It is desirable that the V.O.C. amount be reduced by 20% or less of the total. In order to reduce the viscosity enough for spray gun applications, the spray gun requires a liquid epoxy rather than a solid or semi-solid type. This means that a fast reaction is required in order to cure the liquid resin quickly after the solvent evaporates. We have now discovered that the incorporation of acrylates in the composition and some latent hardeners for acrylic resins and epoxy resins can achieve this. Therefore, the present invention provides a coating composition including one or more hardenable resins containing a free acrylic component and a free or reactive epoxy component in the resin, and a ketone block polyamine type hardener, selected components. After the coating is hardened, more than 50% by weight of hardened epoxy groups and less than 50% by weight of hardened acrylic groups are provided. Ketone-terminated polyamines (sometimes referred to as ketimines) are produced by the condensation of amines and ketones to produce alkylazine (1-alkyl) alkylene compounds. For example, 2 moles of ketone react with diethylene glycol. 3 The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ~ *

(Please read the precautions on the back before ^^ 400 order • f Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 495536 A7 B7

V. Description of the invention (2) β ^ Η H2c · 〇 + H2NCH2CH2NCH2CS2NH2-► ketodiethylene glycol amine R2c = N-CH2CH2NCH2CH2 -n = cr2 + h2o ketone-terminated polyamine water produces a compound, two of which are first-order The amines are capped. In this case, there is still one reactive hydrogen present, and the imine reacts with 1 mole of phenyl glycidyl ether to remove the active hydrogen on the secondary amine: R2c = n-ch2ch2-n-ch2ch2-n = cr2

(Please read the notes on the back first

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This compound has low reactivity when incorporated into the composition. However, due to the hydrolytic instability of the double bonds in these compounds, once the composition is applied, hydrolysis with moisture in the air occurs and the regenerated primary amine provides hardening. The regenerated ketone diffuses to the surface and evaporates. The regenerated amine reacts very quickly with acrylic resins, even at ambient temperatures. This results in rapid curing of the film, thus keeping the film in a position where the epoxy resin is hardened by the amine. The hardener may be derived from a polyamine having 2 to 6 amine groups, preferably a polyamine having 3 to 5 amine groups. The ketone end group may be derived from a ketone of the formula 12000, wherein I and R2 are independently an alkyl group having 1 to 15 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Suitable epoxides include polyglycidyl esters, polyglycidyl ethers, and cycloaliphatic epoxides. The available epoxides are preferably those containing more than one base on average 4 — — This paper size applies to China National Standard (CNS) A4 (210X297 mm), order #f 495536

V. Description of the invention (5)

Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs who are directly connected to oxygen or nitrogen atoms, where R1 represents a hydrogen atom or a methyl group. Examples of this epoxide that can be mentioned are polyglycidyl and poly (Ling-methyl Glycidyl) ester obtained by reacting a compound containing two or more carboxylic acid groups per molecule with epichlorohydrin, dichloropropanol, or / 3-methylepichlorohydrin in the presence of a base . The polyglycidyl ether may be derived from an aliphatic polycarboxylic acid, such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or a dimer or trimer Sesame oil; Derived from cycloaliphatic polycarboxylic acids such as tetrahydropeptidic acid, 4-methyltetrahydropeptidic acid, hexahydropeptidic acid and 'methylhexahydropeptidic acid; and derived from aromatic polycarboxylic acids such as peptides Acid, isophthalic acid and peptidic acid. A further example is polyglycidyl and poly (cardiomethylglycidyl) ether, which consists of a compound containing at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups per molecule and appropriate epichlorohydrin It can be obtained under alkaline conditions, or in the presence of an acid catalyst and subsequent treatment with a base. These ethers can be made from acrylic alcohols, such as from ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol and poly (oxypropylene) glycols, propane_i, 3-diol, butane], 4-diol, poly (oxytetramethylene) glycol, pentane-1.5-diol 'hexanediol' hexane-2,4,6-triol , Glycerol '1,1, L · trimethylolpropane, isoprene tetraol, sorbitol and polyepichlorohydrin; from cycloaliphatic alcohols such as resorcinol, p-cyclohexanediol, bis (4- Hydroxycyclohexyl) methane 5 This paper size applies to Chinese National Standard (CNS) A4 size (210x 297 mm) (Please read the precautions on the back before filling in this page.) == 口

495536 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the Invention (^), 2,2 · bis (4-hydroxycyclohexyl) propane and U-bis (hydroxymethyl) cyclohex-3-ene; and by Alcohols with aromatic nuclei, such as 2,4- (dihydroxymethyl) benzene. They can also be made from mononuclear phenols, such as resorcinol and hydroquinone, and from polynuclear phenols, such as bis (4-hydroxyphenyl) methane, 4,4f-dihydroxydiphenyl-U, 2,2- Four (4-hydroxyphenyl) ethanes, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, and aldehydes Such as formaldehyde, acetaldehyde, chloroaldehyde and furfural and phenols such as phenol itself, and phenols such as chlorophenol, 2-methylphenol and 4_ via a chlorine atom or an alkyl group (each containing up to nine carbon atoms) in the ring. Third butyl phenol, the formed phenolic lacquer resin. Epoxides can also be used, in which all or part of the epoxy groups are unterminated, such as ethylene cyclohexane dioxide, dioxide, dicyclopentadiene dioxide, tetraoxatetracycline [6, 2.1. 02'7.03,5] undec-9-yl glycidyl ether, bis (4-oxatetracyclo [6,2.1.02,7.03'5] undec-9-yl ether or ethylene glycol, 3-4- Epoxycyclohexylmethyl 3W-epoxycyclohexane carboxylic acid ester and its 6,61 dimethyl derivative, ethylene glycol bis (3,4-epoxycyclohexane-carboxylic acid ester) ), 3- ^ 4-epoxycyclohexyl) -8,9-epoxy-2,4-dioxo [5,5] undecane, and epoxidized butadiene or butadiene and Ethylene compounds such as styrene and vinyl acetate. Epoxy resins having U-epoxy groups attached to heteroatoms of different morphology can be used, for example, glycidyl ether-glycidyl ester of salicylic acid. If desired, mixtures of epoxy resins can be used. Preferred epoxy resins are 2,2-bis (4-hydroxyphenyl) propane, bis (4-cotyl) -methyl or methylamine and acids (or a chlorine atom in the ring or one containing one to nine carbons) Phenolic lacquer tree formed by atomic alkane-substituted phenol) (Please read the precautions on the back before filling this page) Clothing-、 1Τ

This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) 495536 (II) Λ7 V. Description of the invention (female) Polyglycidyl esters, polyglycidyl ethers of fat, and at least 0.5 equivalents per kilogram 1,2-epoxide content, and 3,4-epoxycyclohexylmethylepoxycyclohexanecarboxylate. Suitable acrylic resins include compounds containing at least two bases of the formula CH3-COO- where R3 represents a hydrogen or chlorine atom, or a methyl or ethyl group. Suitable esters having at least two groups of formula (Π) include esters, especially aliphatic, cycloaliphatic, cycloaliphatic, araliphatic or heterocyclic aliphatic polyols, especially acrylic acids of glycols and triols Esters and methacrylates; polyhydroxy-, especially dihydroxy-, carboxylic acids; polyhydroxy-, especially dihydroxy, alkylamines; and polyhydroxy-, especially dihydroxy, alkylnitrile. Also available are acrylate-urethane and -urea. The esters are usually commercially available, and may not be prepared by known methods. Suitable acrylic esters include the following formula (please read the notes on the back before filling out this page) 〇 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs CH〇 = CC-0 13 (CH2) x- (CHR4) cCHC I r 〇 II -cc = ch2 b I 〇 (工 工 I) where R3 is as defined above. R5 stands for Η '_CIi3, _C2H5, _CH2OH, or this paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 495536 Λ7 B1 V. Description of the invention (Hand)

• Q • ch2〇-c-och2, R3 R4 represents H, OH or 〇II • 〇CC = CH 'x is an integer from 1 to 8, b is an integer from 1 to 20, and c is zero or 1. Among the compounds of the formula (III), X is preferably 1 to 4, b is 1 to 5, and R3 represents a hydrogen atom or a methyl group. Specific examples of the compound include diacrylates and dimethyl esters of ethylene glycol, propylene glycol, butane-1,4-diol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and tetrapropylene glycol. Acrylate. Other suitable acrylic esters are as follows: (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 〇 “II R3 I II ch2 = cco— [-1-(CH2) dp 0—L 1 c ”b (IV) where b, c, R3, and R4 have the same definitions as above, d is zero or a positive integer if c and d are not both zero, and e is 2, 3, or 4, and This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 495536

V. Description of the invention (7) R6 represents an organic group having a valence e of one of the b oxygen atoms connected via one or more carbon atoms. Preferred compounds of formula (IV) are those in which b, c and d are each 1, R3 is a hydrogen atom or a methyl group, and R6 is a hydrocarbon residue of an aliphatic polyhydric alcohol having 2 to 6 carbon atoms, such as Isopentaerythritol. Specific examples of this compound are four isoprene tetraols (dimethyl glycol acrylate). Other suitable esters are urethane acrylate and urethane acrylate of the following formula "〇〇 一 1 II 9 II 10 CH9 = CC-0-Ry-XC-NH- R 丄 υ 13 (V) 1" g wherein R3 has the above definition, R9 represents a divalent aliphatic, cycloaliphatic, aromatic or araliphatic group, which is connected to the indicated atom and -X-atom or group via one or more carbon atoms thereof, X stands for -〇-, (alkyl)-, where alkyl has 1 to 8 carbon atoms, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page), \ 多 g 系An integer of at least 2 and up to 6, and R1G represents a g-valent cycloaliphatic, aromatic or araliphatic group, bonded to the indicated NH group via one or more carbon atoms thereof. The preferred R9 represents a divalent aliphatic group of 2 to 6 carbon atoms, and R1C? Represents one of the following: a divalent aliphatic group of 2 to 10 carbon atoms, as shown in the following basic paper dimensions applicable to Chinese national standards ( CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495536 Λ7 ______ ^ • 一 ____-- 5. Description of the invention (R) _ (CH2) 6-, CH2C (CH3) 2CH2CH ( CH3) (CH2)-, or -CH2CH (CH3) CH2C (CH3) 2CH2) 2 ': or phenyl, which can be replaced by methyl or chlorine atom if necessary; Benzyl; τ formula -C6H4C6H4 · , C6H4CH2C6H43 ^ C6H4C (CH3) 2C6H4-; or mononuclear alkylcycloalkyl or alkylcycloalkylalkylene with 6 to 10 carbon atoms, such as methylcyclohexyl-2,4-yl, methylcyclohexyl Cyclohex-2,6-yl or 1,3,3-trimethylcyclohex-5-ylmethyl. Specific examples of the compound of formula (V) are 2,4- and 2,6- (bis (2-propenyloxyethoxycarbamido) toluene) and corresponding methacrylic acid compounds. More suitable acrylates The following formula is r3 R13-C (CH2OOC- <L = CH2) 2 (VI) where R3 has the above definition, R11 represents CH3 ·, C2H5-, -CH2OH, or CH 疒 C (R3) COOCH2-, And R12 represents _CH2OH or _ (: ug 2000 (:( 113) = (: 1 ^ 2, especially 1 丄 1-trimethylolpropane triacrylate, isopentaerythritol tetraacrylate and corresponding methyl group) Acrylate. The more suitable acrylic ester is _______10 This paper size applies to China National Standard (CNS) A4 (210X 297 mm) — (Please read the precautions on the back before filling this page)

、 1T 495536 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (R3 I CH2 = CCOOCH2

13 r3

(VII where R3 has the above definition, R13 represents, -CH3 or -CH2C, and R14 represents a tetravalent residue, containing up to 20 carbon atoms, and one or more carbons of the tetracarboxylic acid after removing the four carboxyl groups Rings, each of which represents a -cooch (r13) ch2oocc (r3) = ch2 and -COOH group directly connected to an adjacent carbon atom, R3 and R13 are -H or -CH3, and R14 is an aromatic benzene ring Residues of Group 4 carboxylic acids, especially pyromellitic acid or diphenyl ketone-3,3 ', 4,4'-tetracarboxylic acid. Compounds in which the epoxy group reacts at least partially with an acidic group in an acrylic resin The example is the following:

q fi CH9 = CC-0-CH〇-CH-CH9-0- (CO) Ί k 2 k7 OH 11 This paper size applies to China National Standard (CNS) A4 (210X 297 mm) (Please read the back Note: Please fill in this page again), r8 (Vchuan) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495536 V. Description of Invention (/ c) where C and e have the aforementioned definitions, R7 stands for -H or -CH3, and R8 An organic group representing a valence e is connected via a carbon atom other than the carbon atom of the carbonyl group. More specifically, when c is zero, R8 may represent a residue having 1 to 60 carbon atoms of an alcohol or phenol having an e hydroxyl group. R8 can then represent an aromatic, araliphatic, alkaromatic, cycloaliphatic, heterocyclic, or heterocyclic aliphatic group, such as an aryl group with only one benzene ring, optionally with chlorine, bromine, or 1 to 9 Carbon atom alkyl group substituted, or an aryl group containing two to four benzene ring chains, interrupted by ether oxygen atoms as needed, aliphatic hydrocarbon groups of 1 to 4 carbon atoms, or maple, each benzene ring as required Chlorine, bromine or alkyl groups of 1 to 9 carbon atoms, or saturated or unsaturated straight or branched chain aliphatic groups, which may contain ether oxygen bonds and which may be substituted by hydroxyl groups, especially 1 to 10 Carbon atom saturated or monoethylenically unsaturated straight chain aliphatic hydroxyl group. Specific examples of this group are aryl groups of formula C6H4C (CH3) 2C6H4-, where e is 2 and -C6H4 (CH2C6H3-) rCH2C6H4, where f is 1 or 2, where e is 3 or 4, and formula _CH2CHCH2 or An aliphatic group of -CH2CH (CH2) 3CH2-, wherein e is 3, or formula, (CH2) 4-, -CH2CHdi-CHCH2_, CH2CH2OCH2CH2-, or _ (CH2CH20) 2CH2CH2-, where e is 2. When c is 1, R8 may represent a residue having 1 to 60 carbon atoms of an acid having an e carboxyl group, preferably a saturated or ethylenically unsaturated straight or branched lipid having 1 to 20 carbon atoms. A hydrocarbon group which may be substituted by a chlorine atom and which may be interrupted by an ether oxygen atom and / or a carbonyloxy group (-COO-), or a saturated or ethylenically unsaturated cycloaliphatic or aliphatic of at least 4 carbon atoms Group-Cycloaliphatic Hydrocarbyl ________12 _____ This paper size is applicable to China National Standard (CNS) A4 (210 X Tear mm) ------ · -------- Order ------ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495536 5. Description of the invention ((I) 'It can be replaced by a chlorine atom, or an aromatic compound of 6 to 12 carbon atoms Hydrocarbon group, which may be substituted by a chlorine or bromine atom. More preferred compounds are those of the C series 1, in which R8 represents a saturated or ethylenically unsaturated straight or branched aliphatic hydrocarbon group of 1 to 8 carbon atoms, depending on Need to be substituted by a hydroxyl group, or a saturated or ethylenically unsaturated straight or branched aliphatic hydrocarbon group of 4 to 50 carbon atoms and interrupted by a carbonyloxy group in the chain, Or saturated or ethylenically unsaturated monocyclic or bicyclic cycloaliphatic hydrocarbon groups of 6 to 8 carbon atoms, or ethylenically unsaturated cycloaliphatic_aliphatic hydrocarbon groups of 10 to 51 carbon atoms, or 6 to 8 carbon atoms A mononuclear aromatic hydrocarbon group of atoms. Specific examples of these residues of carboxylic acids are those of the formula _CH2CH2-, CH = CH-, and -C6H4-, where e is 2. R8 may also contain one or more of the above formula ( I) Epoxy. Specific examples of suitable compounds of formula (VIII) are acrylic epoxy resins such as 1,4-bis (2-hydroxy-3 (propenyloxy) propoxy) butane, bis (4- Poly (2-hydroxy-3- (propenyloxy) propyl) ether of methane (bisphenol F), 2,2-bis ('hydroxyphenyl) propane (bisphenol A) and phenol- Formaldehyde phenolic lacquer resin, bis, bis (2-hydroxy-3-propenyloxypropyl) adipate, and methacrylic acid oxy analogues of these compounds. Compounds of formula (VIII) can be prepared, for example, by Acrylic or methacrylic acid reacts with an appropriate amount of epoxy resin to give an acrylated epoxy product or a bifunctional material containing acrylic and epoxy groups. When using acrylic epoxy or bifunctional materials, it can be substituted There is or part of an epoxy resin and / or an acrylic resin. The components of the coating composition are selected so that the coating has 51 to 95% by weight of a hardened epoxy group, and preferably 51 to 80% by weight after hardening. Its 13 scales are applicable to the Chinese National Standard (CNS) A4 specification (21 × 297 mm) ----------.—— uang ------ ^ ------ 0 (please first Read the notes on the back and fill in this page again) 495536 Α7 Β7% Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (/ z) The remaining hardened base is from acrylic base. It should be noted that a part of the hardened epoxy group may be derived from the hardener ', if any reactive hydrogen having a reaction with glycidyl ether is used. Therefore, the coating composition may contain an acrylic resin plus an epoxy resin; an acrylated epoxy resin with or without an epoxy resin; or a bifunctional material with or without another epoxy resin. Use sufficient hardener to react with the acrylic component and any free epoxy components. The actual amount required will vary depending on the particular compound used. If the composition is too viscous to spray, organic solvents can be added. Suitable organic solvents include hydrocarbons, especially aromatic hydrocarbons, such as xylene, and alcohols, such as butanol. The invention is illustrated by the following examples. Examples 1 to 3 were formulated using a liquid epoxy resin based on bisphenol A. The acrylate used is an acrylic epoxy ester, sold by Croda under the trade name UVU100, or urethane acrylate, sold by Radcure / UCB under the trade name Ebeixryl 220. A 4: 1 mixture of xylene and n-butanol was used as the solvent. The hardener is a ketone-terminated polyamine sold by Ciba-Geigy under the trade name Hardener LC 283. The amounts shown in Table 1 are expressed in parts by weight. 14 (Please read the notes on the back before

The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (21 × 297 mm) 495536 Λ7 B7 V. Description of the invention (()) Table 1 Example 1 2 3 1 I — epoxy resin i 100 100 100 UVU 100 30 --Ebercryl 220 _ 30 50 LC 283 56.5 62.7 75.25 Solvent 21.1 22.2 26.7 Each formula can be sprayed and quickly forms a solid film. Example 4 consists of 80 parts by weight of an epoxy diacrylate (which is formed from acrylic acid and a diglycidyl ether of bisphenol A), 20 parts by weight of a 4: 1 mixture of xylene and n-butanol, and 33 parts by weight Hardener LC 283 is formulated. The formulation is sprayable and can be recoated at 201: 3-4 hours and 5 ° C for 3-5 hours. The coating is resistant to friction after 16 hours of methyl ethyl ketone. (Please read the notes on the back before filling this page)

、 1T i0. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 15 This paper size applies to China National Standard (CNS) A4 (210X 297 mm)

Claims (1)

495536j announcement A8 B8 C8 D8 '—I Scope of patent application 1. A coating composition comprising one or more hardenable resins, the resin comprising a free acrylic portion and at least a portion of an acrylic portion of a free or reactive epoxy portion in the resin Present in a fully acrylated epoxy resin or in a bifunctional material containing acrylic and epoxy groups, and derived from an amine with 2 to 6 amine groups and a ketone of the formula Ril ^ CtO, where 1 and R2 A ketone-terminated polyamine type hardener independently having an alkyl group of 1 to 15 carbon atoms. The components of the selected coating composition provide more than 50% by weight of hardened epoxy groups and less than 50% by weight after the coating is hardened. % Hardened acrylic group. 2. The composition as claimed in claim 1 in which any active hydrogen atom remaining in the hardener is reacted with glycidyl ether. 3. The composition according to item 1 of the patent application scope, wherein the epoxy portion is present in epoxy resin, and the epoxy resin is polyglycidyl ester, polyglycidyl ether or cycloaliphatic epoxide. 4. The composition according to item 1 of the application, wherein the epoxy resin is polyglycidyl ether or bisphenol A or bisphenol F. 5. The composition according to item 1 of the scope of patent application, wherein the acrylic portion is present in an acrylic resin, and the acrylic resin is a compound containing at least two groups of the formula CH2 = CR3-COO- (H) β 6 · For example, the composition according to item 1 of the patent application scope, wherein the acrylic resin is an acrylic urethane. 7. As for the composition of the scope of application for patent No. 1, in which at least part of the epoxy part is pre-reacted and partly formed acrylic resin is treated as a full $ paper size applicable to the Chinese National Standard (CNS) A4 specification (210x297 mm) ) (Please read the precautions on the back before filling this page),}!] * &Quot; Line I 495536 A8 B8 C8 D8 VI. Patent application scope Acrylated epoxy resin is treated as fully acrylicized epoxy resin or when As a bifunctional material containing acrylic and epoxy groups. (Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 specifications &lt; 210 X 297 mm)